The occurrence of through-bond orbital interactions in an α,ω donor-acceptor substituted bi(cyclohexylidene) and bi(cyclohexyl)

• Verfasst von: Oosterbaan, Wibren [VerfasserIn]
• Verfasst von: Havenith, Remco W. A. [VerfasserIn]
• Verfasst von: Walree, Cornelis A. van [VerfasserIn]
• Verfasst von: Jenneskens, Leonardus W. [VerfasserIn]
• Verfasst von: Gleiter, Rolf [VerfasserIn]
• Verfasst von: Kooijman, Huub [VerfasserIn]
• Verfasst von: Spek, Anthony L. [VerfasserIn]
• Titel: The occurrence of through-bond orbital interactions in an α,ω donor-acceptor substituted bi(cyclohexylidene) and bi(cyclohexyl)
• Titelzusatz: x-Ray diffraction, UV-Vis absorption and photoelectron spectroscopy, ab initio SCF-MO and natural bond orbital analyses
• Verf.angabe: Wibren D. Oosterbaan, Remco W.A. Havenith, Cornelis A. van Walree, Leonardus W. Jenneskens, Rolf Gleiter, Huub Kooijman and Anthony L. Spek
• E-Jahr: 2001
• Jahr: 11th June 2001
• Umfang: 9 S.
• Fussnoten: Gesehen am 11.11.2020
• Titel Quelle: Enthalten in: Perkin / 2
• Ort Quelle: Cambridge [u.a.] : Royal Society of Chemistry, 1980
• Jahr Quelle: 2001
• Band/Heft Quelle: (2001), 7, Seite 1066-1074
• ISSN Quelle: 1364-5471
• DOI: doi:10.1039/B102410H
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1738414116

Abstract

The ground state σ-π and π-π* interactions in 2-[4-(1-phenylpiperidin-4-ylidene)cyclohexylidene]malononitrile (1) and 2-[4-(1-phenylpiperidin-4-yl)cyclohexylidene]malononitrile (2) have been studied. Both the ionization potentials of 1 and 2, and ab initio RHF/6-31G calculations in combination with a natural bond orbital analysis show that the ground state through-bond interaction (TBI) between the 1-phenylpiperidine electron donor and the dicyanoethylene electron acceptor in 1 and 2 is distinct but small. The olefinic bond in 1 enhances the interaction between the 1-phenylpiperidine electron donor and the dicyanoethylene electron acceptor as compared to 2. The TBI between the N,N-dialkylanilino donor and the olefinic bond in 1 can be modulated by rotation of the phenyl group around the C-N bond. The solid state structures of 1 and 2 have been determined by single crystal X-ray diffraction. In the crystal intermolecular electron-donor-acceptor complexes are formed, which give rise to an intermolecular charge transfer absorption in the solid state.